Sulfamic-substituted di-tertiaryalkyl peroxides



Patented Feb. 20, 1951 SULFAMIC.-SUBSTITUTED Ill-TERT ARY- ALKYL .PEROXIES Frederick F. Rust, Oakland, and Alan R. Stiles and William ;E.Vaughan, Berkeley, (la-lit, assignors' to Shell Development Company, SanFrancisco, Calif., a corporation of Delaware No Drawing. ApplicationFebruary 1.4, 1949, Serial No. 76,406

This invention relates to polyfunctional organic compounds containing aperoxy group, O-O-, attached to two carbon atoms and al o containing thesulfamyl group (--,S.O2NH2) or an N- substituted sulfamyl group attachedto one or more carbon atoms. The invention is directed to the provisionof a novel and valuable series of new compounds, and in a specificembodiment, provides a class of particularly stable organic peroxideshaving unique chemical properties, i. e., monosubstituteddi-tertiary-alkyl peroxides and halogen-containing .di-tertiary-alkylperoxides in which the substituent is a u-linm ll Q2N.H

and alkylsulfamyl, --SO2NH- (alk -yl) or an arylsulfamyl, SO2NI-I(aryl),group.

This application is a continuation-in-part of our .copending applicationSerial No. 792,840, filed December 19, .1947, now U. S. Patent2,519,403. Our earlier filed application describes and claims a novelreaction process by which certain organic peroxides can be sulfohaloenated to form the novel peroxidic sulfonyl halides which are alsodescribed and. claimed therein. This application describes and claimsthe class of novel compounds which can be prepared by treating certainperoxidic sulfonyl halides with nitrogen derivatives which are capableof forming amides of sulfonyl halides, under conditions conducive to theformation of amides.

This invention provides novel sulfamyl-substituted organic peroxidescontaining the peroxy group (-OO) between two tertiary carbon atoms. Ingeneral, the OO- grouping in an organic molecule is so unstable that acomepound containing it, if it reacts under a given set of conditions,undergoes a reaction involving the bonds of this grouping. We have nowdiscovered, however, that when the grouping is contained between twotertiary carboniatoms, not only-can the compound be sulfohalogenated,but derivatives of the sulfonyl halidecan bekformed, and suchderivatives exhibit both the chemical properties characteristic of thederivative and of the particularly stable class of peroxides.

Illustrative examples of the peroxides provided by the present inventioninclude aliphatic peroxides such as 2-methyl-2-tertiary-butylperoxypropanesulfonanilide, bis(phenylsulfamyltertiary-butyl) peroxide,- the N,N-.diethylz2'm thyl- 2tertiary hexylperoxypropane 'snlfonalnides, and 2-methyl-2-(bromo-.-tertiary hutylperoxy) butanesulfonami'de;= aromatic peroxides such'as a,a-dimethylbenzyl '.propylsulfamyl tertiary-ibutyl peroxide,a,a-dimethylbenzyl ..u.-.methylsu1famyl- 'a-methy-lbe'nzyl peroxide,and. .chloIo-tertiary 11 Claims. (Cl. 260-556.)

butylperoxy 1,1-dimethyl-3-sulfamylpropyl peroxide. In thesulfamyl-substituted peroxides of the invention that contain in additionto the sulfamyl group or groups a halogen atom, at least one of only thehydrogen atoms on aliphatic carbon atoms that are bonded to carbon andhydrogen exclusively, is replaced by sulfamyl or N -subst-itutedsulfamyl, as the case may be.

The preferred class of compounds provided by the invention consists ofsubstituted di-tertiaryallcyl and halogen-containing di-tertiary-alkylperoxides in which the substituent groups consis-t of at least onesulfamyl or hydrocarbonsulfamyl group, i. e., in which the definedsulfamyl groups are the only substituents replacing hydrogen atoms ofthe di-tertiary-alkyl and halogencontaining di-tertiary-alkyl peroxides.The preferred class is typified by compounds such as 2- methyl 2-tertiary-butylperoxypropanesulfon amide, I chloro-tertiaryebutylphenylsulfamyltertiary-butyl peroxides, and bis(propylsu1famy1-tertiary-butyl) -peroxide.

The compounds provided by the invention are prepared by treating thecorresponding sulfonyl chloride or bromide by the procedures applicableto the formation of suliamyl and N-substituted suliamyl deriva e o t akyl r aryl ulf y chlorides o br m des Ho e as y oth organic compounds,the compounds provided by the present invention can be prepared by othemetho s o synth s s general, one or more .-SOzCl or -SO2Br groupscontained in an organic peroxide, in which the peroxy group is containedbetween carbon atoms at least one of which is attached to three carbonatoms, can be converted to sulfamyl groups by any nitrogen derivativesuitable for the similar conversion of alkyl or aryl sulfonyl chloridesor bromides. Illustrative examples of the nitrogen derivatives which maysuitably be attachedthrough the S,O2. group in the compound p ovid bythe in i include m A particularly preferred class of compounds providedby the invention are monosubstituted di-tertiary-alkyl peroxides orhalogen-containing di-tertiary-alkyl peroxides in which the substituentis a sulfamyl group and the halogen is chlorine or bromine.

Another particularly preferred class of compounds provided by theinvention are monosubstituted di-tertiary-alkyl peroxides orhalogencontaining di-tertiary-alkyl peroxides in which the substituentis an alkylsulfamyl group and the halogen is chlorine or bromine.

Another particularly preferred class of compounds provided by theinvention are monosubstituted di-tertiary-alkyl peroxides orhalogencontaining di-tertiary-alkyl peroxides in which the substituentis an arylsulfamyl group and the halogen is chlorine or bromine.

A preferred method of preparing the particularly preferred classes ofperoxides comprises the sulfochlorination of a di-tertiary-alkylperoxide, or its halo-analog; by contacting the peroxide with sulfurdioxide and chlorine, in the liquid phase, in the presence of actinicradiations, at a temperature below the decomposition temperature of theperoxide (the process of our earlier filed application); andneutralizing the sulfochlorination reaction mixture with ammonia or aprimary amine or secondary amine. We have found that by following theabove procedural steps, the following equations (illustrated byditertiary-butyl peroxide and ammonia) express substantially the onlyreactions by which the reactants are converted:

actinic light Sort-C12 cmllooocwmnom-soml4:110!

(Where a valuable amine is used, it can be conserved by employing anequimolar amount of a tertiary amine or an inorganic base in place ofone molar portion of the amine.)

Because of the complexity of their structure, specific examples,illustrative of the particularly preferred classes of compounds providedby the invention, can be most clearly presented as the reaction productsobtained in the above manner from: (A) a peroxide such asdi-tertiary-butyl peroxide, chloro-di-tertiary butyl peroxide,ditertiary-amyl peroxide, bromo-tertiary-butyl 1,1- dimethylbutylperoxide and bis(chloro -tertbutyDperoxide; and (B) ammonia or a primaryamine such as methylamine, butylamine, heptylamine, decylamine,isopropylamine, tertiarybutylamine, aniline, m-toluidine andmesitylamine. Amines and peroxides containing not more than 10 carbonatoms are of the molecular size preferred in the production of theparticularly preferred compounds of the invention.

The compounds provided by the invention are especially valuable in thatthey make available for the first time organic peroxides capable ofbeing ionized and containing the peroxy group in the structuralarrangement described above. This arrangement, in which the peroxy groupis contained between two tertiary carbon atoms, has been found to renderthe peroxides containing it more inert to shock, conditions of storage,and the like, than the general class of peroxides in which the group iscontained in other structural arrangements. The preferred class ofcompounds, in addition, provide the first peroxides containing thisadvantageous structural arrangement and having a tendency to be solublein an alkaline medium and insoluble in an acid medium. The increase intheir solubility in ionic media has provided in the present compoundsparticularly valuable reagents for free radical initiated reactions;such as emulsion polymerization reactions and the like, conducted insuch media; and reactions in which a source of oxygen is desired, suchas bleaching processes, which are advantageously conducted in analkaline aqueous medium.

The following examples are presented to illustrate in detail the methodof preparing particular sulfamic-substituted peroxides. As manyvariations in the reactants and reaction conditionsare within the scopeof the invention, the invention is not to be construed as being limitedto the particular compounds specified in the examples.

Example I A sulfonyl chloride suitable for conversion to a sulfonamideprovided by the present invention, is prepared by the followingprocedure. In a. transparent reaction vessel 146 grams (1.0 mole) ofdi-tertiary-butyl peroxide is illuminated by a 500 watt lamp andmaintained at from 6 C. to C. A gaseous mixture of 0.3 mole ofsulfurdioxide with 0.2 mole of chlorine is introduced over a period of1.5 hours. The crude Z-tertiarybutylperoxy-2-methylpropanesulfonylchloride is isolated by distilling off the dissolved gases and unreactedperoxide.

Example II The sulfonanilide of the sulfonyl chloride produced in themanner described in Example I is prepared by slowly adding to 60 gramsof the crude product 24 grams (0.25 mole) of aniline. The product isseparated by filtering the reaction mixture.

The sulfonanilide prepared in the above manner is2-tertiary-butylperoxy-2-methy1propanesulfonanilide M. P. 91.6-92.4" C.

$11: CH: CHFC-O-O--CHx-SOzNHCaHs Ha Ha Example III The sulfonamide ofthe sulfonyl chloride produced in the manner described in Example I isprepared by slowly adding 60 grams of the crude product to a mixture of25 grams of concentrated ammonium hydroxide and 25 grams of ice. Theproduct is separated by filtering the reaction mixture.

The sulfonamide prepared in the above manner is2-tertiary-butylperoxy-2-methylpropanesulfonamide,

H: 7 Hz Example IV A N-aliphatic sulfonamide of the sulfonyl chlorideproduced in the manner described in Example I is prepared by maintainingat about 20 C. a well-stirred mixture of 6 grams of the crude product,3.9 grams (0.03 mole) of dibutylamine and 50 grams of a 10 per centsolution of aqueous sodium hydroxide. The product is separated bycooling and filtering the reaction mixture or by the extractionprocedures applicable to the isolation of an alkyl or aryl sulfonamide.

The product prepared in the above manner is N,N-dibutylZ-tertiary-butylperoxy-Z-methylpropanesulfonamide,

Example VI A sulfamyl-substituted halogen-containing organic peroxideisproduced by pouring 28 grams (0.10 mole) of chloro-tertiary-butylchlorosulfonyl-tertiary-butyl peroxide into a mixture of 30 grams ofconcentrated ammonium hydroxide and 30 grams of ice maintained at 0 C.The product is separated by allowing the mixture to reach roomtemperature and filtering.

The product produced in the above manner is chloro tertiary butylsulfamyl tertiary butyl We claim as our invention:

1. 2-tertiary-butylperoxy-Z-methylpropanesu1- fonanilide.

2. 2-tertiary-butylperoxy-2-methylpropanesulfonamide.

3. 'N,N-dibutyl ,2-tertiary-butylperoxy-2methylpropanesulfonamide.

4. A di-tertiary-alkyl peroxide in which one hydrogen atom is replacedby sulfamyl.

5. A di-tertiary-alkyl peroxide in which one hydrogen atom is replacedby N-alkylsulfamyl.

6. A di-tertiary-alkyl peroxide in which one hydrogen atom is replacedby N-arylsulfamyl.

'7. A di-tertiary-alkyl peroxide in which at least one hydrogen atom isreplaced by SO2NH2.

8. A di-tertiary-alkyl peroxide in which at least one hydrogen atom isreplaced by -SO2N (-alkyl) 2.

9. A di-tertiary-alkyl peroxide in which at least one hydrogen atom isreplaced by -SOzNI-I (aryl) 10. An organic peroxide in which the peroxygroup is directly attached by one bond to a tertiary carbon atom of atertiary alkyl radial and by the other bond to a tertiary carbon atom ofa chlorine-substituted tertiary-alkyl radical, in which peroxide atleast one of only the hydrogen atoms of said first-mentionedtertiary-alkyl radical is replaced by sulfamyl.

11. An organic peroxide in which the peroxy group is directly attachedto a tertiary aliphatic carbon atom in each of two radicals selectedfrom the class consisting of tertiary-alkyl radicals, aralkyl radicalscontaining a tertiary aliphatic carbon atom, and halogen-substitutedtertiaryalkyl radicals, in which peroxide at least one of only; thehydrogen atomson aliphatic carbon atoms that are bonded to carbon andhydrogen exclusively, is replaced by a substituent group selected fromthe class consisting of sulfamyl, N-alkylsulfamyl, and N-arylsulfamyl.

FREDERICK F. RUST.

ALAN R. STILES. WILLIAM E. VAUGHAN.

No references cited.

1. 2-TERTIARY-BUTYLPEROXY-2-METHYLPROPANESULFORNANILIDE.